Bulk metallic glasses are thermodynamically metastable alloys with an amorphous structure that becomes increasingly unstable at temperatures above their glass transition temperature, leading to degradation of their advantageous properties. Thus, enhancing the thermal stability of bulk metallic glasses is critical for preserving their exceptional characteristics. Recently, our team successfully synthesized a Fe₅₉W₂₃B₁₈ (atomic fraction, %) bulk metallic glass that exhibits high thermal stability and further developed a series of (Fe_{1 - x} Cr _x )₅₉W₂₃B₁₈ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) bulk metallic glasses by incorporating Cr in this study. Results show that Cr addition notably enhanced the thermal stability of FeWB bulk metallic glasses, with (Fe_0.9Cr_0.1)₅₉W₂₃B₁₈ achieving a glass transition temperature of 954 K and an crystallization onset temperature of 994 K. This substantial increase in thermal stability is primarily attributed to Cr playing a role in the formation of strong metal-metalloid covalent bonds (Cr—B bonds), which enhance interatomic interactions. Additionally, the substantial presence of an Fe₂₃B₆-like medium-range order structure further stabilized the system. Furthermore, the corrosion resistance of the FeWB bulk metallic glass system was considerably improved by Cr addition, as indicated by an approximately 10-fold reduction in the corrosion current density. This enhancement can be primarily attributed to the formation of a dense Cr₂O₃ passivation layer on the alloy surface. However, the reduced pitting potential of Cr₂O₃ relative to WO₃ led to a slight decrease in the pitting corrosion resistance of the FeCrWB alloys.